Stabilization of synthetic polymers

ABSTRACT

A synthetic polymer composition stabilized against photo- and thermal deterioration thereof wherein there is incorporated, in a sufficient amount to prevent such deterioration, a 4aminopiperidine derivative.

United States Patent [1 1 Murayama et al.

[ 51 Sept. 9, 1975 STABILIZATION OF SYNTHETIC POLYMERS [75] Inventors:Keisuke Murayama; Syoji Morimura; Katsuaki Matsui; Tomoyuki Kurumada;Noriyuki Ohta; Ichiro Watanabe, all of Tokyo, Japan [73] Assignee:Sankyo Company Limited, Tokyo,

Japan [22] Filed: Sept. 21, 1973 [21] Appl. No: 399,611

[52] U.S. Cl 260/45.8 N [51] Int. Cl. C08K 5/34 [58] Field of Search260/45.8 N

[56] References Cited UNITED STATES PATENTS 3,480,635 11/1969 Altwicker260/45.8 N 3,684,765 8/1972 Matsui et all 260/45.8 N

3,705,166 12/1972 Murayama et al 260/45.8 N

Primary Examiner-Melvyn l. Marquis Attorney, Agent, or F irm-Toren,McGeady and Stanger [5 7] ABSTRACT 12 Claims, No Drawings STABILIZATIONOF SYNTHETIC POLYMERS DETAILED DESCRIPTION OF THE INVENTION wherein Rand R represent a lower alkyl group or R and R together with the carbonatom to which they are attached, represents a group 30 R represent analkyl group, a substituted alkyl group, an alkenyl group, an alkynylgroup or an unsubstituted or substituted aralkyl group. n is an integerof l, 2 or 3. When n is 1, R represents a hydrogen atom, an alkyl group,a substituted alkyl group, an alkenyl group, an alkynyl group, asubstituted or unsubstituted aralkyl group, a cycloalkyl group, asubstituted or unsubstituted aryl group, a monoacyl group, analkoxycarbonyl group which may be substituted with hydroxyl, anaralkoxycarbonyl gruop, an N-substituted or unsubstituted carbamoylgroup, an N-substituted or unsubstituted thiocarbamoyl group or amonovalent group from an oxoacid, or R, and R together with the nitrogenatom to which they are attached, represent a phthalimido group.

When n is 2, R, is an alkylene group, an alkenylene group, an aralkylenegroup, an arylene group, a diacyl group, a carbonyl group, anN-substituted dicarbamoyl group, an N-substituted bisthiocarbamoyl groupor a divalent group from an oxoacid, or R and R together with thenitrogen atom to which they are attached, represent a pyromellitodiimidogroup.

When n is 3, R, represents an alkanetriyl group, an aralkanetriyl group,a triacyl group, a trivalent group from an oxoacid, or a group OI 21group (m is an integer of 1-4).

R,-, represents a hydrogen atom, an alkyl group, a substituted alkylgroup, an alkenyl group, an alkynyl group. a substituted orunsubstituted aralkyl group, a cycl oalkyl group, a substituted orunsubstituted aryl group, an alkoxycarbonylalkenyl group, a 5- or6-membered heterocyclic group containing as hetero atom nitrogen, oxygenand/or sulfur or a group CH" CH3 CH CH.

(R is as defined above) or, when R, is an alkylene group, an alkenylenegroup, aralkylene group, an arylene group, an alkanetriyl group, or anaralkanetriyl group, R may be a monoacyl group, an alkoxycarbonyl group,an aralkoxycarbonyl group, a N-substituted or unsubstituted carbamoylgroup, a N-substitued thiocarbamoyl group or a monovalent group from anoxoacid.

German Offenlegungsschrift (application laid open to public insepction)No. 2,040,975 discloses compounds having the following formula as lightstabilizers for synthetic polymers wherein R represents a hydrogen atomor an acyl group; R represents a hydrogen atom, an unsubstituted orsubstituted alkyl group, a cycloalkyl group, an unsubstituted orsubstituted aryl group, an unsubstituted or substituted aralkyl group orthe group of the formula CH, CH,

CH, CH3.

)1 is an integer of l to 3 inclusive; and, when n is 1, R

represents a hydrogen atom, an acyl group, an alkoxy-.

carbonyl group, a carbamoyl group, a thiocarbamoyl group, anN-substituted carbamoyl group, an N- substituted thiocarbumoyl group ora monovalcnt group derived by removing one hydroxyl group from anoxoacid or R may form, together with R the group of the formula when nis 2, R represents a diacyl group, an N- substitut'ed dicarbamoylgroup,an N-substituted bisthiocarbamoyl group, a carbonyl group or'adivalent group derived, by removing two hydroxyl groups, from 4copolymers, ethylenebutene copolymers, ethylenevinyl acetate copolymers,styrene-butadiene copolymers, acrylonitrile-styrenebutadiene copolymersand the like; i

an oxoacid, and, when n is3, R represents a tria cyl polyvinyl chloridesand polyvinylidene chlorides,

group, an N-substituted trica'rbamoyl group, an N- substitutedtristhiocarbamoyl group or a trivalent group derived, by removing threehydroxyl groups, from an oxoacid or a salt thereof.

Moreover, German Offenlegungsschrift No. 2,040,983 discloses compoundshaving the following as light stabilizers for synthetic polymers whereinR a hydrogen atom or a cyano group; R and R may be the same or differentfrom each other and each is a hydrogen atom or a methyl group; X is animino group or an oxygen atom; and R is a hydrogen atom or the group;

It has now been foundthat the 4-aminopiperidine derivatives of formula Iwherein an alkyl group, a substituted alkyl group, an alkenyl group, analkynyl group ,or asubstituted or unsubstituted aralkyl group isintroduced at a nitrogen atom of the piperidine ring have improvedstabilizing effects on synthetic polymers; more particularly theyeffectively prevent photodeterioration, and they do not causediscoloration of the substrates even when blended withstericallyhindered phenol type derivatives commonly utilized asantioxidants, especially BHT (2,6-di-tert. butylhydroxytoluene.

Accordingly, this invention provides 4- aminopiperidinc derivativeshaving the aboveincluding homopolymers of each of vinyl chloride andvinylidene chloride, vinyl chloride-vinylidene chloride copolymer andcopolymers of each of vinyl chloride and vinylidene chloride with vinylacetate or other ethylenically unsaturated monomers;

polyacetals such as polyoxymethylene and polyoxyethylene; polyesterssuch as polyethylene terephthalate; polyamides such as 6-nylon,6,6-nylon and 6,10-nylon; and polyurethanes.

Synthetic polymers have been widely utilized in various forms such asfibers, films, sheets, other shaped articles, latex and foams because oftheir excellent properties.

The lower alkyl groups R and R in the abovementioned formula (I) have 1to 4 carbon atoms and may be, for example, methyl, ethyl or propyl.Preferably R and R are eachflmethyl. Alkyl groups repre sented by R havel to 8 carbon atoms and are, for ex ample, methyl, ethyl, propyl, butylor octyl; substituted alkyl groups R;, have 1 to 3 carbon atoms in thealkyl moiety and are for example, hydroxyalkyl, e.g., 2- hydroxyethyl;alkoxyalkyl having I or 2 carbon atoms in the alkoxy moiety, e.g.,Z-ethoxyethyl or ethoxymethyl, aryloxyalkyl in which the aryl is phenyl,e.g., 2-phenoxyethyl, aliphatic acyloxyalkyl having 2 to 18 carbon atomsin the acyl moiety and aromatic acyloxyalkyl having 7 to l l carbonatoms in the acyl moiety, e.g,, 2acetoxy ethyl, 2stearoyloxyethyl, 2-benzoyloxyethyl or Z-acryloyloxyethyl; halogenoalkyl, e.g.,2-chloroethyl; cyanoalkyl, e.g., 2-cyanoethyl or eyanomethyl;epoxyalkyl, e.g., 2,3-epoxypropyl; aminoalkyl substituted on thenitrogen atom by alkyl groups having 1 to 4 carbon atoms, e.g.,diethylamine methyl; alkoxycarbonylalkyl in which the alkoxy moiety has1 to 4 carbon atoms, e.g., ethoxycarbonylmethyl, butoxycarbonylmethyl,Z-ethoxycarbonylpropyl or 2-methoxycarbonylethyl, oraryloxycarbonylalkyl in which the aryl is phenyl, e.gphenoxycarbonylmethyl; alkenyl groups represented by R have 3 to 4carbon atoms and are, for example, allyl; alkynyl groups R;, have 3 or 4carbon atoms and are, for example Z-propynyl; substituted orunsubstituted aralkyl groups R;, are benzyl which may be substituted byalkyl groups having 1 to 4 carbon atoms or by chlorine atoms on thephenyl part and are. for example, benzyl, pmethylbenzyl orp-chlorobenzyl. According to a preferred embodiment, R represents analkyl group having 1 to 4 carbon atoms, an allyl group, analkoxycarbonylmethyl group in which the alkoxy has l to 4 carbon atoms a2,3-epoxypropyl group, an aliphatic 2 acyloxyethyl group in which theacyl has moiety has 2 to 4 carbon atoms or a benzyl group; mostpreferably R represents the methyl group.

When n is 1, alkyl groups represented by R, l to l8 carbon atoms andare, for example, methyl, ethyl, propyl, isopropyl, n-butyl, hexyl,heptyl, oetyl, dodecyl or stearyl; substituted alkyl groups; alkenyl,the alkynyl and substituted or unsubstituted groups represented by R arethe same as exemplified with regard to the R or3,S-di-tJmtyl-4-hydroxybenzyl; cycloalkyl groups R have 5 or (w carbonatoms and are, for example, cyclohexyl; substituted or unsubstitutedaryl groups R have 6 to carbon atoms in the ,aryl moiety and may besubstituted on said my] by alkyl or alkoxy groups having 1 to 4 carbonatoms and are, for example, phenyl, 0-, mor p-tolyl, 0-, morp-methoxyphenyl or a -or B-naphthyl, monoacyl groups represented by Rare, for example, aliphatic monoacyl groups having 2 to 18 carbon atomse.g., acetyl, propionyl, butyryl, octanoyl, lauroyl, stearoyl,acetoacetyl, 3-octylthiopropionyl. acryloyl, methacryloyl, crotonyl,sorboyl, cinnamoyl, phenylacetyl or 3( 3,5-di-tert-butyl-4-hydroxyphenylpropionyl, cycloaliphatic monoacyl groups having 6 to 7 carbon atoms,e.g., cyclohexanecarbonyl; aromatic monoacyl groups which have 6 to 10carbon atoms in the aryl moiety and which may be substituted on saidaryl by alkyl groups having 1 to 4 carbon atoms, by chlorine, hydroxy ormethoxy groups, e.g., benzoyl, 0-, mor p-toluoyl, 0-,, morp-chlorobenzoyl, salicyloyl, 0-, mor p-anisoyl, p-tert.-butylbenzoyl ora or B-naphthoyl, or heterocyclic monoacyl groups comprising oxygen atomor nitrogen atoms as hetero atoms, e.g,, 2-furoyl, morpholinecarbonyl,isonicotinoyl or nicotinoyl; alkoxycarbonyl groups represented by R. maybe substituted with hydroxyl groups and have 1 to 8 carbon atoms in thealkoxy moiety, for example, ethoxycarbonyl, octoxycarbonyl orZ-hydroxyethoxycarbonyl; aralkoxycarbonyl groups R have benzyl as thearalkyl and are, for example, benzyloxycarbonyl; the substituents ofN-substituted carbamoyl and N- substituted thiocarbamoyl groups R, are,for example, alkyl groups having 1 to 4 carbon atoms, such as methyl orethyl, cyelohexyl, phenyl, chlorophenyl, 01- or B naphthyl orbenzylgroups. If R, is a monovalent group derived from an oxoacid, agroup ismeant which is derived, by removing one hydroxyl group, from asubstituted or unsubstituted sulfenic, sulflnic, sulfonic, phosphorousor phosphoric acid. As examples of such oxoacids there may be mentionedmethanesulfcnic acid, bcnzencsulfenic acid, benzenesulfinic acid,methancsulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid ordiphenyl phosphorous acid,

When n is 2, alkylene groups represented by R. have 2 to 6 carbon atomsand are, for example, ethylene, propylene, tctramethylene orhexamethylene; alkenylene groupsR have 4 to 6 carbon atoms and are,forexample, 2-butenylene; aralkylcne groups R, have 8 to 10 carbon atomsand are, for example, p-xylylene; arylene groups have 6 to 8 carbonatoms and are, for example, p-phenylene or 2,4-tolyene. Diacyl groupsrepresented by R may be aliphatic diacyl groups having 2 to 18 carbonatoms, e.g,, oxalyl, malonyl, succinyl, adipoyl, suberoyl, sebacoyl orfumaryl, aromatic diacryl groups having 8 carbon atoms, e.g.,isophthaloyl or terephthaloyl. cycloaliphatic or and heterocyclic diacylgroups. The substitucnts of N-substituted dicarbamoyl and N-substitutedbisthiocarbamoyl group R, are, for example, alkylenc groups having 2 to6 carbon atoms, cg, butylene or hexamethylene, arylene groups having 6to 8 carbon atoms,, e.g., pphenylene or 2,4-tolylene andp.pGmethanediphenylcne. By By divalent groups R, derived from an oxoacidgroups are meant which are derived, by removing two hydroxyl groups,from asulfurous, sulfuric, substituted or unsubstituted sulfinic,sulfonic, phosphorous or phosphoric acid, Examplcsof such oxoacid are,sulfurous sulfuric, benzene-1,3 disulfonic, phenylsulfurous orphenylphosphoric acid;

When n is 3, alkanetriyl groups represented by R have 5 or 6 carbonatoms and are, for example,

aralkanetriyl groups R have 9 carbon atoms of 9 and are, for exampleTriacyl groups represented by R4 aliphatic triacyl groups having 6carbon atoms, e.g., the propane-1,2,3- tricarbonyl group. aromatictriacyl groups having 9 carbon atoms, e.g., the benzenel,2,4-tricarbonyl or benzenel ,3,5-tricarbonyl group; by trivalent groupsR, derived from an oxoacid groups are meant which are derived byremoving three hydroxyl group, from an oxoacid such as phosphoric,phosphorous or boric acid, for example,

for example, the corresponding groups wherein m is 2. R, preferablyrepresents an alkyl group having 1 to 18 carbon atoms, an allyl gruop, abenzyl group, a 2,3 epoxypropyl group, an aliphatic monoacyl grouphaving 2 to 18 carbon atoms, benzoyl group, a Z-hydroxye thoxycarbonylgroup, an alkylene group having 2'to 6 carbon atoms or an aliphaticdiacyl group having 2 to l8 carbon atoms,

Alkyl, substituted alkyl, alkenyl, alkynyl, substituted or unsubstitutedaralkyl, cycloalkyl, substituted or unsubstituted aryl, monoacyl,alkoxycarbonyl, aralkox- 124. N,N,N"-"l'riacetyl-l ,3,5-tris( 122,6,6-

pentamethyl-4-piperidylaminomethyl )benzene 125.N,N,N-Triacetyl-l,3,5-tris(1,2,2,6,6-pentamethyl-4-piperidylamino)triethylphosphite 126. 4-(Z-Hydroxyethoxycarbonylamino l 2,16,6-

pentamethylpiperidine Furthermore, compounds having the followinggeneral formula (la) are preferred among the compounds represented bythe aforementioned general formula (I) wherein 1 represents 1 or 2, andwhen l is l, R represents a saturated aliphatic monoacyl group having 8to 18 carbon atoms, an unsaturated aliphatic monoacyl group having 3 or4 carbon atoms, or the Z-hydroxyethoxycarbonyl group and when l is 2, Rrepresents a saturated aliphatic diacyl group having 4 to 10 carbonatoms.

The 4-aminopiperidine derivatives (1) of this invention may be easilysynthesized according to the methods shown in the Table below.

N CH1, H R

(III

In the above formulae, R R R R and n are as defined above, R representsa group other than hydrogen but otherwise as defined above for R,-,.

A. In the above table, the reactions, (ll) --0 (IV) and (Ill) (V) or(Vll), may be effected by reductive amination of the starting materialand the corresponding amine according to catalytic reduction. (SeeExample l()).

B. The reactions, (ll) (V), (lV) (V) and (Vl) (Vll may be effected byreacting the starting material with the corresponding halide in thepresence of an acid binding agent. (See Example 1 l) C. Alternatively,the desired product wherein R is methyl may be prepared by reacting thestarting material with formaldehyde and formic acid according toLeuckart reaction, (See Examples 12 and 13) D. The reactions, (IV) (Vl)or (VII) and (V) (VII), may be effected reacting the starting materialwith the corresponding halide in the presence of an acid binding agent(Examples l4 and 15).

The 4-aminopiperidine derivatives (l) employed as stabilizers in thepresent invention may be readily incorporated into the syntheticpolymers by any. of the various standard procedures commonly utilized inthe art. The stabilizer may be incorporated into the synthetic polymerat any desired stage prior to the manufacture of shaped articlestherefrom. Thus, for example, the stabilizer. in the form ofa drypowder. may be admixed with the synthetic polymer, or a suspension oremulsion of the stabilizer may be admixed therewith.

The amount of the 4aminopiperidine derivatives (1) employed in thesynthetic polymer in accordance with the present invention may be variedwidely, depending upon the types, properties and particular uses of thesynthetic polymer to be stabilized. In general, the derivatives may beadded to the synthetic polymer in an amount ranging from 0.01 to 5.07:by weight, based on the amount of the synthetic polymer, but thepractical range is varied depending upon the type of the syntheticpolymer, for instance, 0.01 to 2.0% by weight,

preferably 0.02 to 1.0% by weight for polyolefins, ().()l

to 1.071 by weight, preferably 0.02 to 0.571 by weight for polyvinylchloride and polyvinylidene chloride, and

0.01 to 5.07! by weight, preferably 0.02 to 2.0% by weight forpolyurethanes and polyamides.

The above-mentioned stabilizer may be used in admixture with other knownadditives such as antioxidants, ultraviolet absorbers. fillers, pigmentsand the like.

Such additives are exemplified as follows.

1. Antioxidants .1 Simple 2,6dialkylphenols, such as, for example, 2,-6-di-tert.butyl-4-methylphenol, 2tert.-butyl-4,6- dimethylphenol,2,6-di-tert.-butyl-4- methoxymcthylphenol 2,6-dioctadecyl-4-methylphenol.

.2. Derivatives of alkylated hydroquinones, such as, for example,2.S-di-tert.-butyl-hydroquinone, 2,5-di tert.-amyl-hydroquinone,2,6-di-tert.- butylhydroquinone, 2,5-di-tert.-butyl-4-hydroxyanisole.3,5-di-tert.-butyl-4-hydroxy-anisole and tris-(3,S-di-tert.-butyl-4-hydroxyphenyl)-phosphite, 3,5-di-tcrt.butyl-4-hydroxyphenyl-stearate,di-(3,5-ditert.-butyl-4-hydroxyphenyl )-adipatc.

.3. Hydroxylated thiodiphenyl others. such for ex ample,2,2'-thiobis-(6tert.butyl-4-methylphenol), 2.2 -thiobis-( 4-octylphenol4,4 -thiobis-( 6-tert.- butyl-3-methylphcnol 4,4-thiobis-( 3,6-di-sec.-amylphenol) and 4,4-thiobis-(6-tcrt.-butyl-2 methylphenol 4,4 'Bis(2,6-dimethyl-4-hydroxyphenyl )-disulfide.

l.4. Alkylidene-bisphenols. such as, for example, 2,2-

and

methylcnebis-( o-tert.-butyl-4-methylphenol 2,2' mcthylcne-bis-(o-tert.butyl-4-ethylphenol 4,4-mcthylene-bis-(o-tert.-butyl-2-mcthylphenol 4,4-

.5. 0-, N- and S-benzyl compounds, such as, for example,3,5,3,5-tetra-tert.butyl-4,4'-dihydroxydibenzylether,4-hydroxy-3,S-dimethylbenzyl-mercaptoacetic acid octadecyl ester,tri-(3,5-di-tert.-butyl-4' hydr0xybenzyl)-amine, andbis-(4-tert.-butyl-3- hydroxy-2,6-dimethylbenzyl )-dithiolterephthalate.

.6. Hydroxybenzylated malonic esters, such as, for example,2,2-bis-(3,5-di-tert.-butyl-2-hydroxybenzyl)- malonic acid dioctadecylester, 2-(3-tert.-butyl-4- hydroxy-S-methylbenzyl)-malonic aciddioctadecyl ester, 2,2'bis-( 3,5-di-tert.-butyl-4-hydroxyben2yl malonicacid di-dodecylmercaptoethyl ester and 2,2- bis(3,5-ditert.-butyl-4-hydlroxybenzyl )-malonic aciddi-(4-tert.-octylphenyl )ester.

.7 Hydroxybenzyl-aromatics, such as, for example, 1,-

3 ,5 -tri-(3 ,5 -di-tert.-butyl-4hydroxybenzyl)-2 ,4,6-trimethylbenzene, 1 ,4-di-(3 ,5 -di-tert.-butyl-4-hydroxybenzyD-Z ,3 ,5,6-tetramethylbenzene and 2 ,4 ,6- tri-(3 ,5 -di-tert.-butyl-4-hydroxybenzyl) phenol.

.8 s-Triazine compounds, such as, for example, 2,4-

bis-octylmercapto-6-( 3,5-ditert.butyl-4-hydroxyanilino )-s-triazine,2-octylmercapto-4,6-bis-(3,5-ditert.-butyl-4-hydroxyanilino)-2-triazine, 2-octylmercapto-4,6-bis-( 3,5-di-tert.-butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.-butyl-4-hydroxyphenoxy )-s-triazine, 2,4,6-tris-( 3,5-di-tert.-butyl-4-hydroxyphe1nylethyl)-s-triazine and l,3,5tris-(3,5-di-tert.butyl-4-hydroxybenzyl isocyanurate.

.9 Amides of 3,S-di-tert.-butyl4-hydroxyphenylpropionic acid, such as,for examplel,3,5-tri-(3,5-ditert.-butyl-4-hydroxyphenyl-propionyl)-hexahydro-striazineand N,N-di-( 3,5-di-tert.-butyl-4- hydroxyphenylpropionyl)-hexamethylenediamine.

.10. Esters of 3,5-di-tert.-butyl-4hydroxyphenylpropionic acid withmonohydric or polyhydric alcohols, such as, for example, methanol,ethanol, octadecanol, 1,6-hexanediol; 1,9-nonanediol, ethylene glycol,l,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentylglycol, pentaerythritol, undecanol, 3-thia-pentadecanol,trimethylhexanediol, trimethylolethane, trimethylolpropane, trishydroxyethyl-isocyanurate and4-hydroxymethyl-lphospha-2,6.7-trioxa-bicyclo [2,2,2] octane.

.l l Esters of 5-tert.-butyl-4-li1ydroxy-3-methylphenylpropionic acidwith monohydric or polyhydric alcohols, such as, for example, methanol,ethanol, octadccanol, l,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentylglycol, pentaerythritol, 3- thia-undecanol, 3-thia-pentadecanol,trimethylhexanediol, trimethylolethane, trimethylolpropane,trishydroxyethyl-isocyanurate and4-hydroxymethyl-lphospha-2,6,7-trioxabicyclo [2,2,2] octane. .12. Estersof 3,5-di-tert.-butyl-4-hydroxyphenylacetic acid with monohydric orpolyhydric alcohols, such as, for example, methanol, ethanol,octadecanol, l,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentylglycol, pentaerythritol, 3-thiaundecanol, 3-thia-pentadecanol,trimethylhexanediol, trimethylolethane, trimethylolpropane,trishydroxyethyl-isocyanurate and4-hydroxymethyl-lphospha-2,6,7-tri-oxabicyclo [2,2,2] octane. .l3.Acylaminophenols, such as, for example, N-(3,5-

di-tert.-butyl-4-hydroxyphenyl)-stearic acid amide andN,N'-di-(3,5-di-tert.-butyl-4-hydroxyphenyl)- thio-bis-acetamide. .14.Benzylphosphonates, such as, for example, 3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonic acid dimethyl ester,3,5-di-tert.-butyl-4-hydroxybenzylphosphonic acid diethyl ester,3,5-di-tert.-butyl-4- hydroxybenzyl-phosphonic acid dioctadecyl esterand 5-tert.-butyl-4-hydroxy-3-methylbenzylphosphonic acid dioctadecylester.

.15 Aminoaryl derivatives, such as, for example,

phenyll -naphthylamine, phenyI-Z-naphthylamine,

N.N-diphenyl-p-phenylenediamine, N,N-di-2- naphthyl-p-phenylenediamine,N,N-di-sec.-butyl-pphenylenediamine,

dihydroquinoline, 6-dodecyl-2,2,4-trimethyll ,2-

dihydroquinoline. monoand di-octyliminodibenzyl and polymerised2,2,4-trimethyll ,2-

dihydroquinoline.

2. UV-absorbers and light protection agents 2.1.2(2-Hydroxyphenyl)-benztriazoles, such as, for

example, the 5-methyl-, 3',5-di-tert.-butyl-, 5-tert.- butyl-,5-(l,l,3,3-tetramethyl-butyl)-, 5chloro- 3,5-ditert.-butyl-,5-chloro-3-tert.-butyl-5- methyl-, 3'-sec.-butyl-5-tert.-butyl-,3-[a-methylbenzyl ]-5 '-methyl-, 3 a-methylbenzyl ]-5 '-methyl-5-chloro-, 4-hydroxy-, 4-methoxy, 4-octoxy-, 3,5- di-tert.-amyl-,3-methyl-5'-carbomethoxyethylor 5 -chloro-3 ',5-di-tert.-amyl-derivative.

2.2. 2,4-Bis-( 2 '-hydroxyphenyl )-6-alkyl-s-triazines, such as, forexample, the 6-ethyl-, 6-undecylor 6-heptadecyl-derivative.

2.3 Z-Hydroxy-benzophenones, such as, for example, the 4hydroxy-,4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benZy1oxy-,4,2',4'trihydroxyor 2'-hydroxy-4,4-dimethoxy-derivative.

2.4 l,3-Bis-(2-hydroxy-benzoyl)-benzenes, such as,

for example, l,3-bis-(2'-hydroxy-4-hexyloxybenzoyl )-benzene, l,3-bis-(2-hydroxy-4'-octoxybenzoyl )-benzene and l,3-bis-( 2 '-hydroxy-4-dodccyloxy-benzoyl)benzenc.

2.5 Esters of optionally substituted benzoic acids, such as, forexample, phenyl salicylate, octylphcnyl salicylate, Idi-bcnzoylresorcinol, bis-(4-tert.-butylbenzoyl)-resorcinol,bcnzoyl-rcsorcinol, 3,5-di-tert.- butyl-4-hydroxybenzoic acid2,4-di-tert.-butylphenyl ester, octadccyl ester or2-methyl-4,o-di-tert.- butylphenyl ester.

2.6 Acrylatcs, such as, for example, tx-cyano-B,,B-

diphcnyl-acrylic acid ethyl ester or isooctyl ester,a-carbomethoxy-cinnamic acid methyl ester,a-cyano-B-methyl-p-mcthoxy-cinnamic acid methyl ester or butyl ester andN-(B-earbomethoxy-vinyl)-2-methylindoline.

.7. Nickel compounds, such as, for example, nickel complexes of2,2-thio-bis-(4-tert.-octylphenol), such as the 1:1 and 1:2 complex,optionally with other ligands such as n-butylamine, triethanolamine orN-cyclohexyl-diethanolamine; nickel complexes ofbis-(4-tert.-octylphenyl)-sulphone, such as the 2:1 complex, optionallywith other ligands such as 2- ethyl-caproic acid; nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert.-butylbenzylphosphonic acid monoalkyl esters, suchas the methyl, ethyl or butyl ester, the nickel complex of 2-hydroxy-4-methyl-phenyl-undecyl-ketonoxime and nickel3,S-di-tert.-butyl-4-hydroxy-benzoate.

2.8. Oxalic acid diamides, such as, for example,4,4-dicotyloxyoxanilide, 2,2'-dioctyloxy-5,5-di-tert.-butyloxanilide,2,2 '-di-dodecyloxy-5,5 '-di-tert.-butyloxanilide,2-ethoxy-5-tertiarybutyl-2'-ethyloxanilide, 2-ethoxy-2-ethyl-oxanilide,N,N-bis-( 3- dimethylaminopropyl) oxalamide, mixture of o-and p-methoxyand oand p-ethoxy-di-substituted oxanilides and mixtures of2-ethoxy-5-tert.-butyl-2'-ethyloxanilide with2-ethoxy-2-ethyl-5,4-di-tert.-butyloxanilide.

3. Metal deactivators, such as, for example, oxanilide, isophthalic aciddihydrazide, sebacic acid bisphenylhydrazide, bis-benzylidene oxalicacid dihydrazide, N,N-diacetyladipic acid dihydrazide,N,N-bissalicycloyl-oxalic acid dihydrazide, N,N-bissalicycloyl-hydrazineand N,N-bis-(3,5-di-tert.-butyl- 4-hydroxyphenyl-propionyl)-hydrazine.

4. Phosphites, such as, for example triphenylphosphate, diphenylalkyl-phosphites, phenyl dialkylphosphites, trinonylphenyl-phosphite,triaurylphosphite, trioctadecylphosphite, 3,9-di-isodecyIoxy-2,4,8,10-tetraoxo-3,9-diphospha-spiro[5.5l-undecane and tri-(4-hydroxy-3,5-di-tert.butylphenyl)-phosphite.

5. Compounds which destroy peroxide, such as, for example, esters ofB-thiodipropionic acid, e.g. the lauryl stearyl, myrystryl or tridecylester, salts of 2- mercaptobenzimidazole, e.g. the zinc salt, anddiphenylthiourea.

6. Polyamide stabilizers, such as, for example, copper salts incombination with iodides and/or phosphorus compounds and salts ofdivalent manganese.

7. Basic co-stabilizers, such as, for example, polyvinylpyrrolidone,melamine, benzoguanamine, triallyl cyanurate, dicyandiamide, ureaderivatives, hydrazine derivatives. amines, polyamides, polyurethanesand alkali metal salts and alkaline earth metal salts of highersaturated or unsaturated fatty acids, e.g. Ca stearate, Mg laurate, Naricinoleatc, K palmitate and Zn stearate.

8. PVC stabilizers, such as, for example, organic tin compounds, organiclead compounds and Ba/Cd salts of fatty acids.

9. Nucleating agents, such as, for example, 4-tert.- butylbcnzoic acid,adipic acid and diphenylacetic acid.

10. Other additives, such as, for example, plasticizers, lubricants.e.g. glyccrine monostearate, emulsifiers. antistatic agents,flameproofing agents, pigments, carbon black, asbestos. glass fibres,kaolin and talc.

Such other additives as described above may be advantageously employedin this invention together with the 4-aminopiperidinc derivatives (I) ata ratio of O.53 to l.

Examples 1 to 9 describe synthetic polymer composi- :ions havingincorporated therein 4aminopiperidine The results are shown in Table l.The stabilizers numbered hereinafter are referred to hereinbefore.

Table l Stabilizer Polypro- Highdensity Stabilizer Polypro- HighdensityNo. pylene polyethylene No. pylene polyethylene l 440 hrs. 900 hrs. 6800 hrs. 1680 hrs. 2 540 I I40 8 I780 2660 3 480 940 9 660 I420 4 620I400 I 640 I 360 840 1780 I I 1680 2400 12 I620 2320 61 720 1440 I3 780I420 63 880 I 620 I4 560 I220 65 820 1680 I6 720 I460 66 820 1600 I 8740 I400 67 680 I 280 22 780 I680 68 660 I I 24 540 I 120 69 760 I840680 I280 70 780 I960 26 520 I080 71 740 I920 28 600 I320 72 420 880 29620 1440 7 3 840 I 840 36 880 I840 74 560 I I80 39 460 900 75 660 I I004 I 5 20 980 77 480 940 42 560 I I 78 760 I300 44 540 I060 79 580 I26046 480 880 80 660 I260 47 520 960 8 I 580 I I20 50 520 I I40 82 600 II20 51 540 I140 83 780 I980 54 600 I 180 84 620 I300 55 920 I820 85 5601 I40 56 820 I660 86 580 1 I80 58 520 I I00 87 740 I820 59 640 I I60 88660 I360 89 480 I I80 I I0 700 I520 90 540 I I60 I I I 880 I940 91 460940 I I3 680 I220 93 680 I220 I I4 600 I260 97 840 I760 I I6 660 I I60I00 560 1240 I I8 820 I920 I03 820 I660 I21 580 I280 I07 720 I680 I24640 1240 I08 820 1740 126 I420 I720 I09 720 I400 None 60 400 40derivatives (I) and their stabilizing effects. Examples EXAMPLE 3 10 to15 describe the preparation of some 4- aminopiperidine derivatives (I)of this invention.

EXAMPLE '1 EXAMPLE 2 Into parts of high-density polyethylene [Hi Zex,trade name, twice recrystallized from toluene, available from MitsuiToatsu Chemicals Inc.] was incorporated 0.25 part of a stabilizer ofthis invention. The resulting mixture was blended and molten. The moltenmixture was molded into a sheet with a thickness of 0.5 mm. underheating and pressure.

'I he sheet was exposed to ultraviolet irradiation at 45C in a fademeter and the time when the sheet be came brittle was measured.

Into 100 parts of polystyrene [[Styron, trade name, recrystallized froma mixture of benzene-methanol, available from Asahi-Dow Limited] wasincorporated 45 0.25 part of a stabilizer of this invention. Theresulting mixture was molded at C under pressure into a plate with athickness of 1 mm.

The plate thus formed was exposed to ultraviolet irradiation in afade-meter at 45C for 500 hours. A test 50 piece of the treated platewas tested for color difference by means of a color-differencecolorimeter according to the method prescribed in Japanese IndustrialStandard K-7103, and the change of the yellowness index of the plate wascalculated according to the 55 following equation:

AYI YI Yl wherein AYI means the change of yellowness index. Yl

) means the yellowness index after exposure and Y1.

means the initial yellowness index of a test piece.

The results are summarized in Table 2.

Table 2 Stabilizer Stabiliyer No. Y1 AYI No. Yl AYI Table Z-ContinuedTable 4 Stabilizer Stabilizer E faging l Nu Y!" AY] NO Y1", AY]Stabilizer Retention Retention Retentlon Retention t 5 No. of of of of 65 69 5 ultimate ultimate ultimate ultimate 8 52 +26 87 5.0 +22elongation tensile elongation tensile 1 1 5.1 +2.7 97 4.x 1.9 Strength12 5.2 +24 107 5.0 +2.4 77% 79% 80% 74% 36 4.8 +2.4 108 4.9 +2.14 6 6973 74 68 54 4.9 +2.3 l l l 5.2 +2ll l0 8 7 74 71 7 61 4.8 +2.1 NUHC 47+173 1 1 9 72 72 69 12 73 77 7s 73 36 7| 76 77 73 54 74 70 77 73 (11 797s 7s 74 EXAMPLE 4 63 77 so 72 67 69 76 71 75 68 Into l()() parts of ABSresin [*Kane Ace B- l 2, trade 72 75 81 76 97 7 so 79 7 name, availablefrom Kanegafuchi Chemical industry In 73 82 Co., Ltd.] was incorporated0.5 part of a stabilizer of N011: 17 48 51 this invention, the resultingmixture was kneaded on a kneading roll at l60C for 6 minutes and thenmolded into a sheet with a thickness of about 0.5 mm. EXAMPLE 6 Thesheet was treated in a sunshine weatherometer [m0 100 pans ofpolyurethane resin prepared from for 50 hours and tested with respect tothe retention of polycapmldctone [E 508(), trade name available ultimateelongation and of ultimate tenslle strength as f Th Ni El ll I d i 14]was i well as coloration degree. porated 0.5 part of a stabilizer ofthis invention. The re- The results are shown in Table 3. sultingmixture was heated and melted and then molded into a sheet having athickness of about 0.5 Table 3 mm. The sheet thus formed was exposed toultraviolet irradiation in a fade-meter at C for 15 hours andwcmhummc'cr then tested with respect to the retention of ultimateStabilizer Retention of N I elongation and ultimate tensile strength.

0. Retentlon of clongatlon ILnMlL struigth The results are given inTable 5.

5 687? 75' 35 x 74 so Table 5 12 77 X2 Stahilirer Retention of Retentionof 36 74 7L) No, ultimate ultimate tensile 5 7 3| elongation strc ngths1 72 7s 4() g 63 73 78 5 91% 78% 69 76 so 2 x7 .74 s1 1 l 83 97 72 7912 77 I07 6) 77 3 7 80 10s 77 x2 45 .54 x7 75 111 78 x2 61 91 84 None 5268 83 (19 as 83 87 86 83 97 86 83 w 111 85 82 EXAMPLE 5 None 73 50 Into100 parts of 6-nylon resin [CM 101 I", trade name, available from TomIndustries Inc] wasincor- EXAMPLE 7 porated 0.25 part of a stabilizer ofthis invention. 1 he resulting mixture was heated and melted and then 559 100 Parts of polxvmyl chlomle res!" P molded into a film having athickness of about 0.1 mm. l j truflenamci avmlsble fmm Nlpporl Zeonunder pressure by a compression molding machine. lnunpmatcd parts ofbutyl tm l f 0.5 part of butyl stearate and 0.25 part of a stabilizerThe film thus formed was aged under the following v of this mvent1on.The mixture was kneaded for 5 minagmg condition and thereafter sub ectedto a tensile 61) on I kneading m and 180C and formed into a t test todetermine the retention of tensile strength and Sheet w a thickness of 05 mm The discoloration of elonglmonthe sheet was then observed afterhaving subjected said I. Ultraviolet irradiation in a fade-meter at 45Cfor Sheet 10 aging tcstc'rs as shown below 200 hours M 1. Sunshineweatheromctcr for 300 hours 2. Aging with heating at C for 2 hours in a(ieer's aging tester The results are shown in Table 4.

2. Aging with heating in a Geers aging tester at C for 00 minutes Theresults are shown in Table 6.

Table 6 Table 8-Continued Stabilizer No. Weathcromcter Geers testerStabilizer Polyethylene Polypropylene No. 60C 3 weeks 60C, 4 weeks 5Pale brown Pale yellow 5 12 I, H H

6 v H 36+ I, H I! X I '1 54 I, I, u

( 9 I, H 108+ u n n 87 v 1 I I H H I,

I 1 1 II I 4-Crotonamido-2 2- None Dark brown Dark brown 6(, wtrdmcthy|YQHUW m piperidine BHT EXAMPLE 8 EXAMPLE 1O Into 100 parts of polyesterresin [Ester-G 1 3 trade name, available from Mitsui Toatsu Chemicals,Inc.] y y m ,2. m ylp p r1 m were incorporated 1 part of benzoylperoxide and 0.2 part of a stabilizer of this invention. The resultingmixture was cured by preheating to 60C for 30 minutes and then heatingto 1005C for an additional hour to give a plate with a thickness of 3mm.

The plate thus formed wax exposed to irradiation in a sunshineweatherometer for 60 hours and the change of its yellowness index wasdetermined according to the method described in the above Example 3.

The results are given in Table 7.

Table 7 Stabilizer No. Y1,I -3Y1 None 1.8 +1311 EXAMPLE 9 Into 100 partsof polyethylene 12100GP", trade name, available from Mitsu ToatsuChemicals Inc.] or polypropylene [.lHH-G", available from Mitsu toatsuChemical lnc. twice recrystallized from monochlorobenzene] were added0.25 part ofa stabilizer of this invention and 0.5 part of BHT 26-di-tert.butylhydroxytoluene and the mixture was mixed and melted andmolded into a plate with a thickness of 3 mm under heating and pressure.

The plate was left in a dark place at 60C for 3 or 4 weeks toinvestigate its coloration degree. The results are shown in Table 8. Thestabilizing compounds of this invention do not show any coloration whenblended with BHT.

Table 8 Stabilizer Polyethylene Polypropylene No. (10(1 3 weeks out. 4weeks 5 lill'l Colorless ('olorless h a .7 H

A solution of 12.3 g. of 1-benzyl-2,2,6,6-tetramethyl- 4-piperidone and9.5 g. of butylamine in 200 ml. of methanol was added to a methanolsuspension of a pre viously activated platinum catalyst and catalyticreduction was effected by shaking under a hydrogen pressure of 2-3 kg/cmto absorb about 1.2! of hydrogen. The catalyst was filtered off from thereaction liquid. the mother liquor was concentrated. the residual liquidwas subjected to distillation under reduced pressure to give 14.2 g. ofthe desired product a colorless liquid boiling at 17l174C/3 mmHg. Yield94.0%.

Analysis for C ,H; N

Calculated: C. 79.41%; H, 11.33%; N, 9.26%. Found: C, 79.36%; H, 11.35%;N, 9.23%.

EXAMPLE 1 1 4-Acrylamido-1-al1y1-2,2,6,6-tetramethylpiperidine To 3.3 g.of 4-acry1amido-2,2,6,o-tetramethylpiperidine were added 0.9 g. ofsodium hydroxide, 0.5 g. of sodium iodide and 5 g. of allyl bromide andthe mixture was heated with stirring to 1001 10C. for 10 hours. Aftercooling, a 10% aqueous solution of potassium carbonate was added to thereaction liquid and the mixture was extracted with ethyl acetate. Theethyl acetate solution was dried, concentrated and the residue wasrecrystallized from n-hexane to give the desired product as whitecrystals melting at 134-135C.

Analysis for C H N O:

Calculated: C, 71.95%; H, 10.47%; N, 11.19%.

Found: C, 72.02%, H, 10.54%; N. 11.04%.

EXAMPLE 12 4-Benzamido-1.2 2.(wb-pentamethylpiperidine To 6 ml. of a 30%aqueous formalin solution was added 2.6 g. of 4-benzamido-22,6,6-tetramethylpiperidine and to the solution was added 2 g. of formicacid. The mixture was heated to 8()-90C for 5 hours. After cooling. thereaction liquid was poured into ice water and then a 50% aqueoussolution of potassium hydroxide was added thereto. The crystallinesubstance which separated was recovered by filtration, washed withwater, dried and recrystallized from cyclohexane to give 2.3 g. of thedesired product as white crystals melting at 151-152C. Yield 85.0%.

Analysis for C H N O:

Calculated: C. 74.41%; H, 9.55%; N. 10.21%.

Found: c, 74.46%; H. 9.50%, N, 10.20%

EXAMPLE 1 3 N,N-Distearoyl-N,N-bis( l,2,2,6,6-pentamethyl-4- piperidyl)-ethylenediamine To 10 ml. of a 30% formalin solution in water wasadded 8.7 g. of N,N'-distearoy1-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)ethylenediamine and then 4 g. of 90% formic acidwas added with stirring. The mixture was heated to 80-90C for 5 hours.After cooling, the reaction liquid was poured into ice water. To thissolution was added a 50% aqueous solution of potassium hydroxide toseparate an oily substance, which was then extracted with benzene. Thebenzene solution was washed with water, dried and the benzene wasdistilled off. The residue was cooled to crystallize. Recovery byfiltration and recrystallization from acetone gave 7.1 g. of the desiredproduct as white crystals melting at l921C. Yield 88.8%.

Calculated: C, 77.44%, H, 12.78%, N, 6.23%.

Found: C, 77.36%; H, 12.82%, N, 6.19%.

EXAMPLE 14 4-( N-Acryloylbutylaminol-benzyl-2,2,6,6-tetramethylpiperidine To a solution of 60 g. ofl-benzyl-4butylamino- 2,2,6,6-tetramethylpiperidine in 60 ml. of etherwas added an aqueous solution of sodium hydroxide 1.2 g. of sodiumhydroxide, 5 ml. of water) and to the solution was added a solution of 2g. of acryloyl chloride in 10 ml. of ether with stirring undeice-cooling. Thesolution was left at room temperature for 1 hour andheated under reflux for additional 4 hours. After cooling, the etherlayer was separated, washed with a 5% aqueous solution of sodiumcarbonate and water and dried, and the ether was distilled off. Thecrystalline residue was recrystallized from petroleum benzene to give6.1 g. of the desired product as white crystals melting at l13-1l5C.Yield 85.8%

Analysis for C H N O:

Calculated: C, 77.48%; H, 10.18%, N, 7.86%.

Found: C, 77.54%; H, 10.10%; N, 7.89%.

IR spectrum (Nujol mull): we 1645 cm; v 1607 cm.

EXAMPLE 15 1-Al1yl-4-(N-allylbenzylamino)-2,2,6,6-tetramethylpiperidineTo 5 g. of 4-benzylamino-2,2,6,6-tetramethylpiperidine were added 2.45g. of sodium hydroxide, 1.3 g. of sodium iodide and 9.8 g. of allylbromide and the mixture was heated with stirring to a bath temperatureof l30-140C for 6 hours. After cooling, to the reaction liquid was added50 ml. of a 10% aqueous solution of potassium carbonate and the mixturewas extracted with benzene. The benzene solution was washed with water.dried and subjected to distillation under reduced pressure to give thedesired product as a colorless liquidboiling at 183l 85fC/4 mmHg.

Analysis for C H N Calculated: C. 80.92%; H. 10.50%; N, 8.58%.

Found: C, 80.91%; H, 10.41%; N, 8.76%.

IR spectrum (liquid film): u 1640 cm According to the aforementionedmethods A to D,

the following compounds of the present invention were synthesized.

4-Amino-1,2,2,6,6-pentamethy1piperidine bp 102C/15 mmHg.4-Acetamido-2,2,6,6-tetramethyll-octylpiperidine bp 20921 1C/1.5 mmHg.4-Lauramido-l ,2,2,6,6-pentamethylpiperidine mp 36.538.5C. 1,2,2,6,6-Pentamethy1-4-stearamidopiperidine mp 66.5C.4-Acry1amido-1,2,2,6,6-pentamethylpiperidine mp l29.4-133C.4-Acrylamido-1-cyanomethyl-2,2,6,6-tetramethylpiperidine mp l59160C. 1,2,2,6,6-Pentamethyl-4-phenylacetamidopiperidine mp 136137C,B-Hydroxyethyl piperidylcarbamate mp 112114C 4-Benzylamino-l,2,2,6,6-pentamethylpiperidine bp 1411,47C/2 mmHg.1,2,2,6,6-Pentamethyl-4-( ptoluenesulfonamido )piperidine mp l37l38Cl-Cyclohexyl-3-( l,2,2,6,6-pentamethyl-4- piperidyl)urea mp 157158Cl-Pheny13-[2,2,6,6-tetramethyl-1-(2,3-epoxypropyl )-4-piperidyl lurea mp5862C l-(a-Naphtyl )-3-( 1 ,2,2,6,6-pentamethyl-4- piperidyl )urea mp223225C lEthyl-3-( 1 ,2,2,6,6-pentamethyl-4- piperidyl )thiourea mp147147.5C l-Pheny1-3-( l,2,2,6,6-pentametyl-4- piperidyl)thiourea mp160.5161C 4-(N-Benzoylbenzylamino)-1,2,2,6,6-pentamethylpiperidine mp8384C 1,2,2,6,6-Pentamethyl-4-( N-tosyl-B-hydroxyethylamino)piperidinemp l47l48,C 1,9-Diaza-1,2,2,8,8,9,10,10-octamethyl-4-(N-methylisopropylamino )-spiro[ 5 5 undecane bp 171172C/4rnmHg.l,2,2,6,6-Pentamethyl-4-( N-methylbenzylamino piperidine bp 163C/6 mmHg.N -Methyl-bis( l.2,2.6,6-pentamethyl-4- piperidyl )amine mp 9495C v2.2.6.6-Tctramethyll Z-propynyl )-4-( N-2-propynylbenzylamino)piperidine bp C/0.2 mmHg. lCyanomethyl-4-(N-cyanomethyl-benzylamino 2,2,6,6-tetramethylpiperidine 3 mp 99-l00C1(2-Ethoxyethyl )-4- N 2 ethoxyethyl )benzylamino ]2.2,66-tetramethylpiperidine bp l89l91C/2 mmHg.

l,2,2,6,6-pentamethy1-4- 1 Z-Acetoxyethyl )-4-[ N-( 2-acetoxyethyl)benzylamino1-2.2.6.6-tetramethylpiperidine bp l7(v178C/2mmHg. 1-Ethoxycarbony1methyl-4-(N-ethoxycarbonylmethylbenzylamino)-2.2,6.6-tetramethylpiperidinc hp2()()-205C/5 mmHg. 4-(N-Benzyl-p-methylbenzylamino)-2.2.6.6-tetramethyl-1-p-methylbenzylpiperidine bp 264-267C/3 mmHg. 4-(N-Benzyl-p-chlorobenzylamino l-pchlorobenzyl-2,2,6.-tetramethylpiperidine bp 281282C/1 mmHg.

l,3-Bis( 1,2,2,6,6-pentamethyl-4-piperidyl )urea mp 174-176C N,N'-Bis(l,2,2,6,6-pentamethyl-4- piperidyl )sebacamide mp 176l77C 1,1 -Bis(l,2,2,6,6-pentamethyl-4-piperidyl)-3.3'-

hexamethylenediurea mp 222223C 1,1 '-Bis(l,2,2,6,6-pentamethyl-4-piperidyl)-3,3'-

(2,4-tolylene )-diurea mp 238238.5C N.N'-Dibenzyl-N,N'-bis(1,2,2,6,6-pentamethyl-4- piperidyl )sebacamide mp l4l142CN,N-Dimethyl-N,N'-bis( l,2,2,6,6-pentamethyl- 4- piperidyl)ethylcnediamine mp 8()81C N,N'-Dimethyl-N,N"bis(1.2.2,6,6-pentamethyl-4- piperidyl )hcxamethylenel ,o-diamine bp2l62l9C/l mmHg.

4-Methacrylamidol ,2,2,6,6-pentamethylpiperidine mp 123.5 124.5c 14-Crotonamidol .2,2,6,6pentamethylpipcridine mp 133"135C- 4-(N-Acetylal1ylamino)- 1 ,2,2,6,6-pentameth y1- piperidine 1 hp l55l58C/6mmHg. 4-( N-Acetyl-2-propynylaminol ,2,2,6,6-pentamethylpipcridine 7 mpl()81()9C4-(Z-Hydroxyethoxycarbonylamino)-1,2,2,6,6-pentamethylpiperidinc mp 114C What is claimed is:

1. A synthetic polymer composition stabilized against photoand thermaldeterioration wherein there is incorporated from 0.01 to 5.0 percent byweight, based on the weight of the synthetic polymer, of a compoundhaving the formula (1) wherein R and R each represent methyl or R, and Rtogether with the carbon atom to which they are linked representa grouphaving the formula R represents alkyl having 1 to 8 carbon atoms;substituted alkyl having 1 to 3 carbon atoms in the alkyl moiety andwhich is selected from the group consisting of hydroxyalkyl, alkoxyalkylhaving 1 or 2 carbon atoms in its alkoxy moiety, phenoxyalkyl, aliphaticacyloxyalkyl having 2 to 18 carbon atoms in the acyl moiety, aromaticacyloxyalkyl having 7 to l 1 carbon atoms in the acyl moiety,halogenoalkyl, cyanoalkyl, epoxyalkyl, aminoalkyl substituted by alkylhaving 1 to 4' carbon atoms, alkoxycarbonylalkyl having 1 to 4 carbonatoms in the alkoxy moiety and phenoxycarbonyl-alkyl; alkenyl having 3or 4 carbon atoms; alkynyl having 3 or 4 carbon atoms or benzyl thephenyl radical of which can be substituted by alkyl having 1 to 4 carbonatoms or by chlorine,

n represents the integer 1, or 3, I R represents, when n is 1, hydrogen,alkyl having 1 to 18 carbon atoms; substituted alkyl, alkenyl, alkynylor unsubstituted or substituted benzyl as de fined under R;,;3,5-di-tert-butyl-4-hydroxybenzyl; cycloalkyl having 5 or 6 carbonatoms; aryl having 6 to 10 carbon atoms in the aryl and which may besubstituted on said aryl by alkyl or alkoxy having 1 to 4 carbon atoms;aliphatic monoacyl having 2 to 18 carbon atoms; cycloaliphatic monoacylhaving 6 or 7 carbon atoms; aromatic monoacyl having 6 to 10 carbonatoms in the aryl moiety and which can be substituted on saidaryl byalkyl having 1 to 4 carbon atoms, chlorine, hydroxyl or methoxy;

heterocyclic monoacyl containing 0- or N-ato ms; al koxyca rbonyl having1 to 8carbon atoms in the alkoxy moiety and which can be substituted byhydroxyl; benzyloxycarbonyl; carbamoyl and thiocarbamoyl which" areunsubstituted or substituted on the N-atom by alkyl having l to 4 carbonatoms cyclohexyl, phenyl, chlorophenyl, naphthyl or benzyl; a monovalentgroup which is derived, by removing a hydroxyl group, frommethanesulfenic acid, benzcnesulfenic acid, benzenesulfinic acid,methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid ordiphenyl-phosphorus acid. or, R and R together with the nitrogen atom towhich they are linked, represent a phthalimido group;

R, represents. when n is 2, alkylene having 2 to 6 carbon atoms,alkenylene having 4 to 6 carbon atoms, aralkylene having 8 to 10 carbonatoms, p.p'- methancdiphcnylene, carbonyl. aliphatic diacyl having 2 to18 carbon atoms, aromatic diacyl having 8 carbon atoms; N-substituteddicarbamoyl or N-suhstitutcd bis-thiocar1mmoyl which are substituted byalkylene having 2 to 6 carbon atoms, arylcnc having (w to 8 carbon atomsor p,pmcthancdiphenylcne; a divalent group derived, by removing twohydroxyl groups, from sulfurous acid. sulfuric acid, benzene-l,3-disulfonic acid, phenylsulfurous acidor phenylphosphoric acid; or, R.and R,-,,'together with the nitrogen atom to which they are linked,represent a pyromellitdiimido group;

R, represents, when n is 3, an alkanetriyl group having or 6 carbonatoms; an aralkanetriyl group having 9 carbon atoms; an aliphatictriacyl group having 6 carbon atoms; an aromatic triacyl group having 9carbon atoms, or'a trivalent group derived, by removing three hydroxylgroups, from phosphoric acid, phosphorous acid or boric acid, or a grouphaving the formulae wherein m represents an integer from l to4; and

R represents hydrogen; a substituted alkyl group, an alkenyl or alkynylgroup, or an unsubstituted or substituted benzyl group as defined underR; an unsubstituted alkyl group, a cycloalkyl group, an unsubstituted orsubstituted aryl group as defined under R an alkoxycarbonylalkenyl grouphaving 1 to 4 carbon atomsin the alkoxy moiety and 2 or 3 carbon atomsin the alkenyl moiety; a 2-thiazolyl- 2-pyridylor Z-pyrimidyl group or agroup having the formula ICH CH,

or, when R represents an alkylene, alkenylene, aralkylene, alka netriylor aralkanetriyl group, R represents an acyl or alkoxycarbonyl group asdefined under R an unsubstituted or N-substituted carbamoyl orthiocarbamoyl group as defined under R or a monovalent group as definedunder 2. A synthetic polymer composition as claimed in claim 1 wherein Rand R each represent methyl.

3. A synthetic polymer composition as claimed in claim 1 wherein R; isan alkyl group having I to 4 carbon atoms, an allyl group, analkoxycarbonylmethyl group having I to 4 carbon atoms in the alkoxymoiety, a 2,3-epoxypropyl group, an aliphatic acyloxyethyl group having2 to 4 carbon atoms in the acyl moiety or a benzyl group.

4. A synthetic polymer composition as claimed in claim 1 wherein R,represents an alkyl group having 1 to 8 carbon atoms, a 2,3-epoxypropylgroup, an allyl group, a benzyl group, an aliphatic monoacyl grouphaving 2 to 18 carbon atoms, a benzoyl group, the2-hydroxyethoxycarbonyl group, an alkylene group having 2 to 6 carbonatoms or an aliphatic diacyl group having 2 to 18 carbon atoms.

5. A synthetic polymer composition as claimed in claim 1 wherein Rrepresents hydrogen, an alkyl group having 1 to 8 carbon atoms, thehydroxyethyl, phenyl, cyclohexyl or benzyl group.

6. A synthetic polymer composition as claimed in claim 1 wherein n is aninteger of l or 2.

7. A syntheticpolymer composition as claimed in claim 1 wherein there isincorporated a compound having the formula wherein n represents aninteger of l or 2, and, when n is 1, R represents a saturated aliphaticmonoacyl group having 8 to [0 carbon atoms, an unsaturated aliphaticmonoacyl group having 3 or 4 carbon atoms or the 2-hydroxyethoxycarbonylgroup, and, when n is 2, R represents a saturated aliphatic acyl grouphaving 4 to 10 carbon atoms.

8. A synthetic polymer composition as claimed in claim 1 'wherein'saidpolymer is a polyolefin.

9. A synthetic polymer composition as claimed in claim 1 wherein saidpolymer is a polyvinyl chloride.

10. A synthetic polymer composition as claimed in claim I wherein saidpolymer is a polyurethane.

11. A synthetic polymer composition as claimed in claim 1 wherein saidpolymer is a polyamide.

12. A synthetic polymer composition as claimed in claim 1 wherein saidcompound of formula I is selected from the group consisting ofl,2,2,6,6-pentamethyl-4- stearamidopiperidine, 4-acrylamido-l,2,2,6,6-pentamethylpiperidine,4-methacrylamido-1,2,2,6,6-pentamethylpiperidine, 4-crotonamido-l,2,2,6,6-pentamethylpiperidine, and 4-( 2- hydroxyethoxycarbonylamino l,2,2,6,6-pentamethylpiperidine.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. ,90 8Dated September 9,1975

Inventofls) KEISUKE MURAYAMA, S MORIMURA. K. MATSUI eta] It is certifiedthat error appears in the aboveidentified patent and that said LettersPatent are hereby corrected as shown below:

In the heading of the patent, insert -[30] Foreign Application PriorityData Oct.4,l972 Japan .99599/72 Signed and Scaled this twenty-third Dayof December 1975 [SEAL] Arrest:

RUTH C. MASON Commissioner ofParenIs and Trademarks

1. A SYNTHIC POLYMER COMPOSITION STABILIZED AGAINST PHOTO- AND THERMALDETERIORATION WHEREIN THERE IS INCORPORATED FROM 0.01 TO 5 PERCENT BEWEIGHT, BASED ON THE WEIGHT OF THE SYNTHETIC POLYMER, OF A COMPOUNDHAVING THE FORMULA (1)
 2. A synthetic polymer composition as claimed inclaim 1 wherein R1 and R2 each represent methyl.
 3. A synthetic polymercomposition as claimed in claim 1 wherein R3 is an alkyl group having 1to 4 carbon atoms, an allyl group, an alkoxycarbonylmethyl group having1 to 4 carbon atoms in the alkoxy moiety, a 2,3-epoxypropyl group, analiphatic acyloxyethyl group having 2 to 4 carbon atoms in the acylmoiety or a benzyl group.
 4. A synthetic polymer composition as claimedin claim 1 wherein R4 represents an alkyl group having 1 to 8 carbonatoms, a 2,3-epoxypropyl group, an allyl group, a benzyl group, analiphatic monoacyl group having 2 to 18 carbon atoms, a benzoyl group,the 2-hydroxyethoxycarbonyl group, an alkylene group having 2 to 6carbon atoms or an aliphatic diacyl group having 2 to 18 carbon atoms.5. A synthetic polymer composition as claimed in claim 1 wherein R5represents hydrogen, an alkyl group having 1 to 8 carbon atoms, thehydroxyethyl, phenyl, cyclohexyl or benzyl group.
 6. A synthetic polymercomposition as claimed in claim 1 wherein n is an integer of 1 or
 2. 7.A synthetic polymer composition as claimed in claim 1 wherein there isincorporated a compound having the formula
 8. A synthetic polymercomposition as claimed in claim 1 wherein said polymer is a polyolefin.9. A synthetic polymer composition as claimed in claim 1 wherein saidpolymer is a polyvinyl chloride.
 10. A synthetic polymer composition asclaimed in claim 1 wherein said polymer is a polyurethane.
 11. Asynthetic polymer composition as claimed in claim 1 wherein said polymeris a polyamide.
 12. A synthetic polymer composition as claimed in claim1 wherein said compound of formula I is selected from the groupconsisting of 1,2,2,6,6-pentamethyl-4-stearamidopiperidine,4-acrylamido-1,2,2,6,6-pentamethylpiperidine, 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine,4-crotonamido-1,2,2,6,6-pentamethylpiperidine, and4-(2-hydroxyethoxycarbonylamino)-1,2, 2,6,6-pentamethylpiperidine.